FR2831180A1 - Two-component dishwasher detergent composition comprises a detergent component and a water softener component - Google Patents

Abstract

Two-component dishwasher detergent composition comprises a detergent component capable of forming an aqueous detergent bath with specified pH range, a water softener component capable of forming an aqueous bath with a predetermined pH range prior to formation of the detergent bath. Two-component dishwasher detergent composition comprises: (a) a detergent component capable of forming an aqueous detergent bath with a pH of 8-12; and (b) a water softener component capable of forming an aqueous bath with a pH of 3.5-6.5 prior to formation of the detergent bath. An Independent claim is also included for a method for avoiding and/or eliminating the deposition of calcium precipitates on dishes, comprising washing the dishes in an automatic dishwasher using the above composition.

Description

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TWO-COMPONENT SOLID FORMULATION FOR AUTOMATIC WASHING OF DISHES AND METHOD OF WASHING
AUTOMATIC DISHWASHER
The present invention relates to a two-component solid detergent formulation for washing dishes in domestic or collective automatic machine, as well as the process using said formulation; the formulation or the method of the invention has the advantage of avoiding the phenomenon of deposition of calcium precipitates (filming), as well as having a curative effect of descaling the dishes and the heating elements and the inner walls of the machine .

 The phenomenon of calcareous filming (veil or deposit on dishes), which is particularly harmful to the appearance of the dishes (and its hygiene), especially for glassware, is a cumulative phenomenon which becomes visible after several consecutive washings. same items of dishes (usually after 3 to 10 washes depending on the hardness of the water used).

This phenomenon is due to the precipitation of insoluble calcium salts, especially calcium carbonate from calcium bicarbonate, under the disjoint or joint actions of the temperature rise during washing and rinsing, as well as the alkaline pH of the washing phase; the compositions are indeed alkaline for the needs of washing performance and non-corrosion of materials.

 The visual detection of the filming by accumulation of washes is explained by a conventional phenomenon of nucleation / growth of calcium and / or magnesium salt crystals.

It could be envisaged to stop this cumulative phenomenon of filming by destroying the nuclei of calcium and / or magnesium salts before they grow and become visible, by treating the articles covered with nuclei by an acid solution able to redissolve these nuclei in the form of soluble salts, this between the rinsing cycle and the drying cycle of the program of the washing apparatus. The disadvantage of such a process is its complexity, which requires the use of at least two separate products to be used in two separate phases of the program of the dishwashing machine.

 The Applicant has found that the problem of filming could be solved by inserting an acid treatment phase before the main alkaline wash cycle, by implementing a single detergent formulation in a single phase of the usual program of the automatic machine. washing

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 dishes. Another advantage of the invention is that said formulation and the method are effective even in hard water.

 Machine wash detergent tablets comprising a compacted detergent core coated with adipic acid or a CsCl3 dicarboxylic acid have already been proposed, in order to form a moisture barrier and to improve the stability of certain additives of the detergent core, such as bleaches and enzymes (EP-A-846,754, EP-A-846,755, EP-A-846,756). The amount of acid that this coating represents does not exceed 10% of the total weight of the tablet.

Unit doses of detergent composition packaged in a pouch divided into two separate compartments for washing clothes in the machine have already been proposed (NL-B-170 308). Said sachet comprises: - an acidic compartment containing a solid acid capable of forming water-soluble salts and / or calcium and magnesium complexes, said compartment being made of a material permeable to cold water capable of releasing the acid to form a pH medium of 2 to 5; and an alkaline compartment containing an alkali metal carbonate and a cleaning composition, said compartment being made wholly or partially of a material that is likely to become permeable to water or to rupture at a temperature of 50.degree.
40 to 60 ° C., to liberate the carbonate and the cleaning composition and form a pH bath of 9 to 10.5 before the temperature reaches 60 ° C.

 A first subject of the invention consists of a two-pack solid detergent formulation for dishwashing in the machine, comprising: a detergent part (W) in solid form capable of forming an aqueous detergent bath with a pH of 8 to 12, preferably from 8 to 11 and * an ant limescale portion acid (A) in solid form capable of forming an aqueous bath with a pH of 3.5 to 6.5, preferably 4.5 to 6, most preferably 5.2 to 6 , prior to the formation of said detergent bath, when said formulation is implemented under the conditions of use (working conditions) of the dishwashing machine.

 The solid-form detergent portion (W) of the two-component formulation of the invention may be any conventional solid detergent composition for machine dishwashing.

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It can be in the form of a powder, pearls or preferably tablet.

The percentages of additives of the detergent part (W) mentioned below are expressed by weight of dry matter relative to the weight of detergent composition (solid detergent part) expressed in sec.

 Among the usual additives used in conventional solid detergent compositions for dishwashing in the machine, there may be mentioned in particular: surfactants in an amount ranging from 0.5 to 10%, preferably of the order of 1 to 5; % among these we can mention: anionic surfactants (0 to 5%) of the alkali metal soap type (alkaline salts of CS-C24 fatty acids), alkaline sulfonates (C 8 -C 18 alkyl benzene sulfonates, C 12 -C 16 alkyl sulfonates), C 6 fatty alcohols -C16 oxyethylenated and sulphated, C 2 -C 18 alkylphenols oxyethylenated and sulfated, alkali sulfosuccinates (C 12 -C 16 alkylsulfosuccinates) ...

*) nonionic surfactants (0.2 to 5%) of the alkylphenol type in
Polyoxyethylenated C6-C12, polyoxyethylenated and / or polyoxypropylenated C8-C22 aliphatic alcohols, ethylene oxide-propylene oxide block copolymers, optionally polyoxyethylenated carboxylic amides, etc.

agents improving the surface properties of surfactants (builders), basifying agents, sequestering agents or auxiliary cleaning agents, such as: Soluble inorganic phosphates of alkali metals, in particular alkali metal tripolyphosphates (0 to 70%), alkali metal metasilicates and silicates (0 to 30%), alkali metal carbonates, bicarbonates or sesquicarbonates, tetraborates of alkali metals (0 to 50%), the cogranulates of alkali metal hydrous silicates and alkali metal (sodium or potassium) carbonates rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868 (0 80%, preferably 20 to 80%); . water-soluble phosphonates and aminophosphonates (ethane-1-hydroxy-1,1-diphosphonates, methylene diphosphonate salts, etc.) such as those of the range BRIQUEST &commat; RHODIA (0 to 2%); . the water-soluble salts of carboxylic polymers or copolymers (0 to
10%), such as the water-soluble salts of polycarboxylic acids with a molecular weight of about 2,000 to 100,000, obtained by polymerization or

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 copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and most particularly polyacrylates with a molecular mass of around 2,000 to 10,000 (US Pat. No. 3,308,067), copolymers of acrylic acid and maleic anhydride with a molecular mass of about 5,000 to 75,000 (EP-A-66 915); . polyacetic acid salts such as nitriloacetic acid, N, N-dicarboxymethyl-2-aminopentane dioic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid (0 to 10%); . soluble salts of citric acid, gluconic acid or tartaric acid (0 to 30%); bleaching agents of the perborate or percarbonate type, whether or not associated with acetylated bleaching activators such as N, N, N ', N'tetraacetylethylenediamine (TAED) or chloroisocyanurate-type chlorinated products (0 to 30%); fillers of the sodium sulphate, sodium chloride type in a proportion of 0 to 50% of the total weight of the said composition, expressed as dry matter; - other various additives such as enzymes (up to 10%), perfumes, dyes, corrosion inhibitors of metals ...

compaction assistants, such as polyethylene glycols, or tablet disintegration.

 The solid detergent portion (W) of the two-component formulation of the invention may optionally further comprise an agent for delaying its dissolution, in order to facilitate the prior formation of an acid scale-scale bath.

Among the agents capable of delaying the dissolution of the detergent part, mention may be made of the salts of poorly soluble fatty acids such as sodium or calcium stearate (0 to 3%, preferably from 0.5 to 1.5%) .

 When the detergent part (W) is in tablet form, it can be conventionally obtained by pressing into a mold the desired amount of an articular detergent composition containing the various constituents of the detergent part. The usual compaction pressures are around 20 to 25 kg / cm 2. A slightly higher compaction pressure, for example from 25 to 30 kg / cm 2, can make it possible to delay the dissolution of the detergent part.

 The acid limescale portion (A) in solid form may be in the form of a compacted powder or not; preferably it comes under

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 form of one or two layers of compacted powder adhering to the detergent portion (W) in tablet form described above.

 The limescale part (A) mainly comprises a solid acid limescale agent (aa) having a melting point of at least 80 C and a solubility of at least 15 g in town water at its feed temperature (from 5 to 25 ° C).

Among the calcium antifreezing agents (aa) that may be used, mention may be made of aliphatic polycarboxylic acids, especially dicarboxylic acids, such as oxalic, adipic, succinic or glutaric acids or their mixtures, as well as common acids. in household descalers such as citric, tartaric and sulphamic acids.

Preferably, the antilime agent (aa) is adipic acid and / or a mixture of adipic, succinic and glutaric (AGS) acids. The melting point of adipic acid is of the order of 150 ° C., its solubility is about 20 g / l in tap water at a temperature of the order of 15 to 25 ° C., and about 100g / l at a temperature of about 60 C.

 Preferably, the limescale part (A) comprises from 60 to 90% of its weight of antilimic acid agent (aa).

It furthermore comprises one or more other solid additives, chosen in particular from those making it possible to facilitate its dissolution in cold water, to complex the calcium ions or to facilitate the compaction or disintegration of the limestone part.

Among these other additives, mention may be made of: * disintegrating and / or effervescent agents in an amount of about 5 to 30% of the weight of the anti-lime part (A), such as. hydrocolloids of hydrophilic and water-swellable plant origin, such as starch and its derivatives, carboxymethylcellulose, sodium acetate, urea, maleic acid, citric acid, carbamic acid, sugars. alkali metal bicarbonates, in particular sodium, water-retaining polymers and copolymers which swell in contact with water, such as cross-linked alkali metal polyacrylates * solubilizing agents capable of improving the dissolution rate of the ant limescale agent (aa), such as liquid polyethylene glycols with a molecular weight of less than 800 g / mol or solid polyethylene glycols with a molecular mass greater than 1000 g / mol, in an amount of about 5 to 10% by weight of the part antilime (A).

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sequestering agents in an amount of the order of 2% to 10% of the weight of the anti-limestone part (A), such as water-soluble phosphonates and aminophosphonates (ethane 1-hydroxy-1,1-diphosphonates, methylene diphosphonate salts,. ..) like those of the range BRICKS) of RHODIA.

The limescale part (A) may further comprise one or more additives helping to shape it (lubricating agents, compacting agents, release agents, etc.)
Most preferably, the anti-scale acidic portion (A) of the two-component formulation of the invention comprises: from 60 to 90% of its weight of antifail agent acid (aa), adipic acid and / or mixture of acids adipic, succinic and glutaric (AGS) in particular. from 5 to 30% of its weight of at least one effervescent and / or disintegrating agent, * from 2 to 10% of its weight of at least one sequestering agent, phosphonate and / or aminophosphonate, in particular
The amount of antilimecaire acid (aa) of the formulation of the invention is such that by dissolution in the water introduced into the dishwasher, a pH of 3.5 to 6.5, preferably 4.5 at 6, especially 5.2 to 6 is obtained in one to two minutes and maintained for 3 to 5 minutes, after the start of the cycling pump of the dishwasher.

The calcium antilime agent (aa) present in the antilime part (A) of the formulation of the invention may represent from 12 to 30%, preferably from 12 to 25% by weight relative to the total weight of the two-component formulation of the invention. Traditionally, detergent tablets for household appliances have a mass of the order of 22 to 30g, said household appliance operating with a volume of wash water of the order of 4 to 8 liters.

 The acid limescale portion (A) and the detergent portion (W) of the two-component formulation of the invention are distinct but not isolated from each other.

Thus, said two-component formulation of the invention may be a pre-dosed two-component system comprising a detergent portion (W) in the form of a tablet, and an acid limescale portion (A) in the form of a fine powder, all of which is contained in a tear-off bag before being introduced into the dishwasher by the consumer; . a two-component, pre-dosed system comprising a detergent part (W) in the form of a tablet, and an acid limescale part (A) in the form of a fine powder contained in an open cavity of the tablet,

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 the whole being contained in a tear-off bag before being introduced into the dishwasher by the consumer; a system identical to the previous ones, the tablet and powder unit being contained in a bag made of a material with a high speed of redissolution in water (in polyvinyl alcohol for example); . a pre-dosed two-component system comprising a detergent part (W) in the form of a breakable tablet or provided with a fragile lid, and an acid limescale part (A) in the form of a fine powder contained in an internal cavity of the tablet, the tablet being cut or fractionated at the lid at the time of introduction into the dishwasher by the consumer; a double or multi-layered tablet, one or more of the layers being constituted by the anti-limescale acid part (A) adhering to one or more layers of detergent part (W) of lower dissolution rate.

 The shaping of the two-component formulation of the invention in the form of multilayer tablets can be carried out conventionally.

 The bicomponent solid detergent formulation which is the subject of the invention can be favorably used in a dishwashing appliance at the rate of 22 to 30 grams per 4 to 8 liters of washing water.

The supply water can be as well softened city water (0 to 10 hardness French TH) than a hard water (20 to 450 French TH, or even more, TH = 4mg of Ca ++ per liter). The temperature of the feed water is generally of the order of 5 to 250 ° C at the inlet of the washing apparatus; it is generally of the order of 60 C at the end of the washing cycle. The formulation of the invention is particularly interesting in hard water, including in extreme conditions (beyond 450 TH).

 The two-component formulation of the invention has a sequential dissolution kinetics, with two distinct phases, first an acid phase of pH 3.5 to 6.5, preferably 4.5 to 6, most preferably , 2 to 6 obtained in one to two minutes and maintained for 3 to 5 minutes after starting the cycling pump of the dishwasher and an alkaline phase whose pH is between 8 and 12, preferably between 8 and 11, for a limited time by normal draining of the dishwasher at the end of the wash cycle.

 This sequenced kinetics has many advantages.

Indeed, the presence of an acid phase prior to the washing phase makes it possible to solubilize the Ca ++ ions of the feed water and thus:

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 . to use in the washing phase phosphate-free detergent compositions and / or to reduce the sequestering level of the detergent compositions in the washing phase.

Said acid phase also has a descaling effect of the scaled dishes introduced into the machine, as well as heating elements and inner walls of said machine.

An improvement in the removal of dirt has also been noted.

 It is particularly advantageous to use a two-component formulation in which the limescale part (A) comprises a phosphonate or a water-soluble sequestering aminophosphonate (2 to 10% of the weight of the limestone part); said phosphonate or aminophosphonate complex Ca ++ ions of the feed water, the acid not completely consumed in the acid phase being converted in the wash phase into a water-soluble alkaline salt with sequestering property (sodium adipate for example); this alkaline salt remaining, after draining the washing water, at least partially on the dishes and the walls of the machine in the form of a film, retains its sequestering properties during the rinsing cycle.

 A second object of the invention consists of a method for preventing and / or eliminating the deposition of calcium precipitates on the dishes, by washing the dishes in an automatic washing apparatus, using an effective amount of one two-component solid detergent formulation comprising a detergent portion (W) in solid form capable of forming an aqueous detergent bath with a pH of 8 to 12, preferably 8 to 11, and an acid ant limescale portion (A) in solid form capable of forming an aqueous bath of pH 3.5 to 6.5, preferably 4.5 to 6, most preferably 5.2 to 6, prior to the formation of said detergent bath.

The amounts and conditions of use of said solid detergent formulation have already been described above.

 The following examples are given for illustrative purposes.

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The composition of the formulations A, B and C used to prepare the 24 g tablets used in the examples is as follows:

<Tb>
<tb> Formulation
<tb> two-component <SEP> A
<tb> Part <SEP> acid <SEP>%
<tb> Adipic acid <SEP><SEP> 85
<tb> HEDP * <SEP> 5
<tb> Na <SEP> Bicarbonate <SEP> 10
<tb> Part <SEP> detergent <SEP>% <SEP> Formulation <SEP> B <SEP> Formulation <SEP> C
<tb> Classic <SEP><SEP> running <SEP>
<tb> Cogranules <SEP> 50 <SEP> Cogranules <SEP> 45 <SEP> Cogranules <SEP> 45
<tb> carbonate / silicate <SEP> carbonate / silicate <SEP> carbonate / silicate
<tb> Nabion <SEP> 15 ** <SEP> Nabion <SEP> 15 ** <SEP> Nabion <SEP> 15 **
<tb> Carbonate <SEP> of <SEP> 13 <SEP> Carbonate <SEP> of <SEP> 6 <SEP> Carbonate <SEP> of <SEP> 8
<tb> sodium <SEP> sodium <SEP> sodium
<tb> Citrate <SEP> of <SEP> sodium <SEP> 15 <SEP> Citrate <SEP> of <SEP> sodium <SEP> 25 <SEP> Citrate <SEP> of <SEP> sodium <SEP> 25
<tb> Polyacrylate <SEP> of <SEP> 5 <SEP> Polyacrylate <SEP> of <SEP> 5 <SEP> Polyacrylate <SEP> of <SEP> 5
<tb> sodium <SEP> sodium <SEP> sodium
<tb> (mass <SEP> 4500) <SEP> (mass <SEP> 4500) <SEP> (mass <SEP> 4500)
<tb> Perborate <SEP> of <SEP> 10 <SEP> Perborate <SEP> of <SEP> 10 <SEP> Perborate <SEP> of <SEP> 10
<tb> sodium, <SEP> 1 <SEP> H20 <SEP> sodium, <SEP> 1 <SEP> H20 <SEP> sodium, <SEP> 1 <SEP> H20
<tb> Activator <SEP> TAED <SEP> 5 <SEP> Activator <SEP> TAED <SEP> 5 <SEP> Activator <SEP> TAED <SEP> 5
<tb> Enzymes <SEP> 2 <SEP> Enzymes <SEP> 2 <SEP> Enzymes <SEP> 2
<tb> HEDP * <SEP> 2
<Tb>
* HEDP: Hydroxyethyl diphosphonate sodium salt ** Nabion15: cogranules of sodium carbonate and sodium silicate marketed by RHODIA

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Exemple 1 comparatif - Etape 1 de dépôt de film à l'aide de la formulation C- Dans un lave vaisselle de marque Bosch (dont on a éliminé les résines échangeuses d'ions) alimenté avec de l'eau de ville présentant une dureté totale de 45 Th, on procède à 5 lavages cumulés de verres initialement propres (cycles "éco" à 60Oc) en utilisant la formulation C (une tablette de 24g à chaque lavage).

Comparative Example 1 - Step 1 of film deposition using the formulation C- In a Bosch dishwasher (which was removed the ion exchange resins) fed with tap water having a total hardness of 45 Th, 5 cumulative washes of initially clean glasses ("Eco" cycles at 60Oc) are carried out using Formulation C (a tablet of 24g each wash).

After the 5 complete washes, strongly filmed glasses having a very visible calcareous veil are obtained. The stainless steel resistances and walls of the dishwasher are also covered with a white limestone voikle.

 - Step 2 washing with the calssic formulation BOn puts the glasses in the dishwasher; a new washing cycle is carried out with a tablet (24 g) of conventional formulation B, without changing the water hardness conditions. After this new washing, it is found that there was no elimination of the veil on the glasses or on the walls and the heating resistance of the dishwasher.

EXAMPLE 2 With the acid part and the detergent part of the formulation A of the invention, 3-layer tablets consisting of. 3. 5g of acidic part. 17 g of detergent part. 3. 5 g of acidic part Repeat step 1 of Example 1.

The glasses are put back in the dishwasher; a new washing cycle is carried out with a tablet (24 g) of bicomponent formulation A of the invention, without changing the water hardness conditions. After this new wash, we see that the glasses are translucent and the walls and the resistance of the dishwasher are no longer covered with limestone. Here we note a curative effect of the formula according to the invention, both on the limestone installed on the glasses and on the washing machine.

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EXAMPLE 3 10 cumulative washes of initially clean glasses (water of 45 Th, eco cycles at 60 ° C.) are carried out using the two-component formulation A according to the invention (24 g tablet at each wash cycle).

It is found that after 10 washes, the glasses do not have a calcareous veil and there is no veil on the walls of the dishwasher. This shows the preventive effect that is sustainable over time and regardless of the number of cycles of cumulated washing carried out in hard water.

Comparative Example 4 10 cumulative washes of initially clean glasses (water of 45 Th, eco cycles at 60 ° C.) were carried out using the conventional formulation B (24 g tablet at each wash cycle).

The glasses are examined after each end of the cycle.

It is found that there is no formation of sails until the 50 cycle; a film appears from the 60 cycle and then increases gradually to become very visible after the cycle.

Claims (16)

1) Two pack solid detergent formulation for machine dishwashing, comprising: a detergent portion (W) in solid form capable of forming an aqueous detergent bath having a pH of 8 to 12, preferably 8 to 11, and a portion anticalcaire acid (A) in solid form capable of forming an aqueous bath with a pH of 3.5 to 6.5, preferably 4.5 to 6, especially 5.2 to 6, prior to the formation of said detergent bath when the said formulation is used under the conditions of use of the dishwashing machine.  2) Formulation according to claim 1, characterized in that the detergent part (W) is a conventional solid detergent composition for washing dishes in the machine.  3) Formulation according to claim 1) or 2), characterized in that the detergent part (W) is in the form of a powder, pearls or tablets.  4) Formulation according to any one of claims 1) to 3), characterized in that the anti-limestone part (A) comprises a solid acid antilime agent (aa) having a melting point of at least 80 C and a solubility of at least 15g / 1 in tap water at the supply temperature.  5) Formulation according to claim 4), characterized in that the antilimic acid agent (aa) is an acid or a mixture of aliphatic polycarboxylic acids, preferably dicarboxylic C2-C6, or a household descaling acid selected from the acids citric, tartaric and sulphamic.  6) Formulation according to claim 5), characterized in that the limescale agent (aa) is adipic acid and / or a mixture of adipic acid, succinic and glutaric acid (AGS). <Desc / Clms Page number 13>  7) Formulation according to any one of claims 4) to 6), characterized in that the anti-limestone part (A) comprises from 60 to 90% of its weight of the antilime agent acid (aa).  8) Formulation according to claim 7, characterized in that the limescale part (A) comprises: from 60 to 90% of its weight of antilimic acid agent (aa),. from 5 to 30% of its weight of at least one effervescent and / or disintegrating agent, from 2 to 10% of its weight of at least one sequestering agent.  9) Formulation according to any one of claims 4) to 8), characterized in that the limescale part (A) is from 12 to 30%, preferably from 12 to 25% by weight relative to the total weight of the formulation Two component.  10) Formulation according to any one of claims 1) to 9), characterized in that the limescale part (A) is in the form of a compacted powder or not.  11) Formulation according to any one of claims 1) to 10), characterized in that the acid limescale part (A) and the detergent part (W) are distinct but not isolated from each other.  12) Formulation according to claim 11), characterized in that it is in the form of a two-component system, pre-dosed, comprising a detergent part (W) in the form of a tablet, and an acid limescale part (A) in the form of a a fine powder, the whole being contained in a tear-off bag before being introduced into the dishwasher by the consumer; of a two-component system, pre-dosed, comprising a detergent part (W) in the form of a tablet, and an acid limescale part (A) in the form of a fine powder contained in an open cavity of the tablet, the whole being contained in a tear-off bag before being introduced into the dishwasher by the consumer; a system identical to the previous, the tablet and powder assembly being contained in a bag of a high-speed material redissolution in water; <Desc / Clms Page number 14>  of a two-component, pre-dosed system comprising a detergent part (W) in the form of a breakable tablet or provided with a fragile operculum, and an acid limescale part (A) in the form of a fine powder contained in an internal cavity of the tablet, the tablet being cut or fractionated at the lid at the time of introduction into the dishwasher by the consumer; * A double or multi-layer tablet, one or more of the layers being formed by the limescale portion (A) adhering to one or more layers of detergent portion (W) of lower dissolution rate.  13) Formulation according to any one of claims 1) to 12), characterized in that it is carried out in a household dishwashing apparatus at a rate of 22 to 30 grams for 4 to 8 liters of water of washing.  14) A method for preventing and / or eliminating the deposition of calcium precipitates on the dishes, by washing the dishes in an automatic washing apparatus, using an effective amount of the two-component solid detergent formulation subject of any one of claims 1) to 12).  15) The method of claim 14), characterized in that said two-component formulation is carried out at a rate of 22 to 30 grams per 4 to 8 liters of wash water.  16) A method according to claim 14) or 15), characterized in that the feed water of the washing apparatus is fresh water or hard water.